Process for the in-solvent, in-situ generation of haloalkyl alkyl ethers

ABSTRACT

The present invention is directed to a process for the preparation of certain N-substituted-2-haloacetanilides via the reaction of a secondary 2-haloacetanilide with a haloalkyl ether, particularly, halomethyl ethers, which comprises forming the ether in situ by the in-solvent reaction of an alcohol, formaldehyde or other aldehyde and an acid halide to produce high purity haloalkyl ethers, while decreasing the concentration of undesirable bis by products, as for example bis(chloromethyl) ether. The ether formed in situ thereafter reacts with the secondary 2-haloacetanilide in the presence of a phase transfer catalyst and base to form the N-substituted-2-haloacetanilide.

This is a division, of application Ser. No. 133,720 filed Mar. 25, 1980and now U.S. Pat. No. 4,284,564.

BACKGROUND OF THE INVENTION

Although there are a variety of methods known in the art to producechloromethyl methyl ether (see e.g. U.S. Pat. No. 3,972,947 and U.S.Pat. No. 3,833,602) and it is known to produce 3-haloalkyl halomethylether (see U.S. Pat. No. 2,916,522) these methods have inherentdisadvantages and often require several manipulative steps which resultsin an increased cost of the process. Thus, a simple method of producinghaloalkyl ethers in high yield which may be used without separation,while decreasing the concentration of undesirable bis(haloalkyl) ethersand especially bis(chloromethyl) ether is highly desirable.

DESCRIPTION OF THE INVENTION

In one aspect, the present relates to an in solvent, in situ process forpreparing haloalkyl ethers having the formula ##STR1## where R₁ ishydrogen or alkyl containing 1 to 4 carbon atoms; X is chloro, bromo oriodo; R is alkyl containing 1 to 10 carbon atoms, alkenyl containing 3to 10 carbon atoms, cycloalkyl containing 3 to 10 carbon atoms, alkynylcontaining 3 to 10 carbon atoms, (C₁₋₅) alkoxy (C₂₋₅) alkyl, mono-halo(C₂₋₅) alkyl, mono-halo (C₃₋₅) alkenyl or ##STR2## where y is theinteger 2, 3, or 4, with the proviso that when R is alkenyl or alkynylthe carbon atom attached to the oxygen atom may not share a double ortriple bond with an adjacient carbon atom; which comprises reacting analcohol of the formula

    ROH                                                        (II)

(where R is as defined above) with an aldehyde of formula ##STR3##(where R₁ is as defined above) in the presence of an acid halide and inthe presence of a solvent.

The above described reaction may be schematically illustrated as:##STR4##

The term "acid halide" as used herein, refers to agents which arecapable of liberating a halide ion in situ; such agents are for thepurposes of this invention, compounds of the formula

    HX

where X is chloro, bromo or iodo, or compounds of the formula ##STR5##where X is as defined above and R₅ is C₁₋₅ alkyl, phenyl, benzyl orsubstituted derivatives thereof. Inorganic halogenating agents such asthionyl chloride, thionyl bromide, sulfuryl chloride, sulfuryl bromide,phosphorous trichloride, phosphorus pentachloride, and the like may alsobe used.

The preferred acid halides for use herein are HCl, HBr, HI, ##STR6##especially preferred is ##STR7##

When acetyl chloride or acetyl bromide is employed as the "acid halide"the corresponding methyl acetate produced is compatable with the desiredhaloalkyl ether product, such that it is not necessary to separate thehaloalkyl ether from the methyl acetate, thus avoiding excessivehandling of the toxic ethers. If desired, the haloalkyl ether may beseparated from the ether product by distillation procedures well knownin the art.

The term "alkyl" includes both straight chain and branched chain alkylgroups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, sec.-hexyl,n-heptyl, n-oxtyl, n-nonyl, n-decyl and the like. Unless otherwiseindicated, preferred for use herein are straight chain and branchedchain alkyl groups containing 1 to 5 carbon atoms.

The term "alkenyl" refers to both straight chain and branched chainalkenyl groups containing 3 to 10 carbon atoms of the type --C_(n)H_(2n-1), e.g., --CH₂ --CH═CH₂, --CH₂ CH₂ CH═CH₂, ##STR8## and the like;preferred for use herein are those alkenyl groups containing 3 to 5carbon atoms.

C₃₋₁₀ Cycloalkyl refers to a monocyclic, saturated hydrocarbon radical,and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclooctyl and the like.

The term "alkynyl" refers herein to a group of the type --C_(n) H_(2n-3)containing 3 to 10 carbon atoms and includes both straight chain andbranched chain groups such as --CH₂ C.tbd.CH, --CH₂ CH₂ C.tbd.CH,##STR9## and the like. Preferred for use herein are alkynyl groupscontaining 3 to 5 carbon atoms.

The term "alkoxyalkyl" refers to a straight chain alkyl group containing2 to 5 carbon atoms substituted on the terminal carbon by an alkoxygroup containing 1 to 5 carbon atoms, e.g., methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec.-butoxy, tert-butoxy, n-pentoxy and the like.

The term "mono-haloalkyl" or "mono-haloalkenyl" refers herein to astraight chain alkyl or alkenyl group containing 2 to 5 carbon atoms or3 to 5 carbon atoms reprectively, and substituted by one halogen atom,i.e., chloro, bromo, iodo or fluoro atom, as for example, chloroethyl,bromoethyl, fluoroethyl, chloropropyl, bromopropyl, chlorobutyl,bromobutyl, chloropentyl and the like. The radical ##STR10## refers tosuch groups as, for example, ##STR11## and the like.

In the practice of the process, described herein, a solid, liquid orgaseous form of aldehyde is preferred. Aqueous solutions of aldehydeshould be avoided as the presence of water in the reaction tends toinhibit formation of the haloalkyl ether and thus reduce yield. Forexample, paraformaldehyde or gaseous formaldehyde is preferred toprepare halomethyl ethers.

The above described process employes a solvent which must meet therequirements of being substantially inert to any of the above reactantsor products and must possess appropriate solubility for the reactantsand products. Suitable solvents include: ethers, for example, ethylether, dioxane, tetrahydrofuran, and isopropylether; hydrocarbons, forexample, benzene, hexane, cyclohexane, toluene, and chlorinatedsolvents, for example, methylene chloride, chloroform, dichloroethane,and carbon tetrachloride. The preferred solvent for use in the presentinvention is methylene chloride.

The presence of solvent in the reaction accomplishes several purposes.In the first instance, the solvent acts to keep the haloalkyl ether inthe organic layer and away from the water formed during the reaction.This is desirable since, as previously noted, the yield of high purityhaloalkyl ether is reduced by the presence of water in the mixture. Thesolvent also acts to dilute and thus reduce the concentration of theundesirable bis(halomethyl) ether by-products formed during the reactionand also provides the reaction medium for the production of theN-substituted-2-haloacetanilide derivatives described below.

As described above, one aspect of the present invention is directed to aprocess for producting a wide range of haloalkyl ether. Yet anotheraspect of the present invention is directed to the preparation ofcertain N-substituted-2-haloacetanilides via a "one pot" or continuousprocess which comprises the steps of:

(1) Forming a halomethyl ether in situ, in a solvent;

(2) Mixing a secondary 2-haloacetanilide and phase transfer catalystwith the mixture of Step 1; and

(3) Reaction of excess base with the mixture of Step 2.

Specifically, the invention relates to a "one pot", batch or continuousprocess for preparing a compound of the formula ##STR12## where X₁ ischloro, bromo or iodo; R is C₁₋₁₀ alkyl, C₃₋₁₀ alkenyl, C₃₋₁₀cycloalkyl, C₃₋₁₀ alkynyl, C₁₋₅ alkoxy (C₂₋₅) alkyl, mon-halo (C₂₋₅)alkyl, mono-halo (C₃₋₅) alkenyl or ##STR13## where y is the integer 2,3, or 4, with the proviso that when R is alkenyl or alkynyl the carbonatom attached to the oxygen atom may not share a double or triple bondwith an adjacient carbon atom; R₂ is equal to C₁₋₈ alkyl, C₂₋₈ alkenyl,C₃₋₈ alkynyl, C₁₋₈ alkoxy, C₁₋₈ alkoxy (C₁₋₅) alkyl, halo (C₁₋₅) alkyl,halogen, NO₂, C₁₋₅ alkoxy (C₁₋₅) alkoxy or C₁₋₅ alkoxy (C₁₋₅) alkoxy(C₁₋₅) alkoxy; R₃ is equal to hydrogen, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₁₋₈alkoxy, C₁₋₈ alkoxy (C₁₋₅) alkyl, halo (C₁₋₅) alkyl, halogen or NO₂ ; R₄is equal to C₁₋₈ alkyl, halo (C₁₋₅) alkyl, halogen or NO₂ ; n is equalto zero, one or two; which comprises reacting, in a solvent and in thepresence of a phase transfer catalyst, an alcohol of the formula

    ROH                                                        (V)

(where R is as defined in Formula IV above), formaldehyde, an acidhalide and a compound of the formula ##STR14## (where X₁, R₂, R₃, R₄ andn are as defined in Formula IV above); followed by addition of excessbase.

The above reaction may be schematically illustrated ##STR15##

The term "haloalkyl" in Formula IV, used in conjuction with the groupsR₂, R₃ and R₄ refers to an alkyl group containing 1 to 5 carbon atoms,such group being substituted by one or more halogen atoms, e.g.,chloromethyl, bromoethyl, dicloroethyl, trichloromethyl,trifluoromethyl, pentafluoroethyl, iodomethyl and the like. "Haloalkyl"as used herein specifically includes trifluoromethyl.

In Formula IV above, the terms "C₁₋₅ alkoxy (C₁₋₅) alkoxy" and "C₁₋₅alkoxy (C₁₋₅) alkoxy (C₁₋₅) alkoxy" includes both straight chain andbranched chain alkoxy groups and includes such groups as for example,--OCH₂ OCH₃, --OCH₂ OC₂ H₅, --OCH₂ CH₂ CH₃, --OCH₂ --OCH₂ CH₂ --OCH₃,##STR16## --(CH₂)₄ --O--(CH₂)₃ CH₃ and the like.

The term "base" refers to a base sufficiently strong enough to reactwith the secondary amide, i.e. the 2-haloacetanilide of Formula VI, toproduce incremental concentrations of amide anion.

It will be understood that the weaker the acidity of the amide ofFormula VI the stronger must be the base. Thus, e.g. weakly acidicamides such as, e.g., 2'6'-dimethyl-2-chloroacetanilide or2',6'-diethyl-2-chloroacetanilide require strong bases such as aqueousor solid sodium hydroxide or potassium hydroxide. Further, it ispreferred when aqueous caustic is used that the solution becontentrated, i.e. 10-50%. On the other hand, where the amide of FormulaVI is strongly acidic, such as, e.g., 2',6'-dinitro-2-chloroacetanilidea weaker base such as solid or aqueous sodium carbonate can be used tosuccessfully generate amide anion.

Bases found to be useful in the above-described process, depending ofcourse on the acidity of the secondary amide of Formula VI are alkalimetal hydroxides, carbonates, and phosphates and alkaline earthhydroxides, e.g., calcium oxide or hydroxide, trisodium phosphate,potassium carbonate. The alkali metal hydroxide bases, i.e., NaOH or KOHare preferred for use herein.

Useful phase transfer catalysts for use herein are those containingorganic-soluble cations such as those enumerated in U.S. Pat. No.3,992,432, including ammonium, phosphonium and sulfonium salts.Exemplary phase transfer catalysts include quaternary ammonium salts,e.g., aryl or aralkyl trialkyl ammonium halide salts such as benzyltriethyl ammonium bromide or chloride. Other phase transfer catalystsinclude the acyclic and cyclic poly ethers which complex with the basecation and then pair with amide anion as couter ion for transport to theorganic phase for alkylation. Exemplary of such catalysts would include"18-crown-6" cyclic ether in combination with potassium hydroxide orfluoride as base.

The ratios of reactants in the above described processes are notcritical, but are dictated primarily by economic considerations andavoidance of unwanted by-products. Hence, large excesses or deficienciesof any expensive component relative to another component should beavoided. It is preferred however, that an excess of base be used.

The process of this invention may be carried out at temperatures rangingfrom subzero to ambient or higher, e.g., from -20° to +100° C., butusually room temperatures are sufficient, and desirable. The temperatureof the reaction is preferably carried out at from 10° to 50° C. Theprocess may be carried out under any convenient pressure, either aboveor below atmospheric.

The process can be carried out either batch wise or continuously. Forexample, continuous operation the alcohol, aldehyde, acid halide,secondary anilide and phase transfer catalyst maybe introduced into astream of solvent at a first reaction zone; excess base may thereafterbe introduced into the mixture at a second reaction zone located at apoint downstream from the first reaction zone.

The following examples illustrate in greater detail the process of thisinvention wherein an N-substituted 2-haloacetanilide is prepared via thereaction of a secondary 2-haloacetanilide and a halomethyl ether, saidether being formed in situ.

EXAMPLE 1 Preparation of2'-Methoxy-6'-Methyl-N[(2-methylbutoxy)methyl]-2-chloroacetanilide

8.8 g. (0.1 moles) of 2-methylbutanol and 1.5 g. (0.05 moles) ofparaformaldehyde were added to 100 ml. of methylene chloride and themixture chilled. To the chilled mixture was added, with stirring, 6.1 g.(0.05 moles) of acetyl bromide. Stirring was continued until allparaformaldehyde dissolved. To this mixture was added 4.7 g.) 0.022moles) of 2'-methoxy,6'-methyl-2-chloroacetanilide and 2.2 g. of phasetransfer catalyst in 50 ml. of methylene chloride. Thereafter, 50 ml. of50% NaOH was added in one portion and the solution was stirred for 5hours, at which time 100 ml. of cold H₂ O was added to facilitateseparation of the organic/aqueous layers. The layers were separated andthe organic layer was washed once with H₂ O, dried over MgSO₄,evaporated and Kugelohr distilled, 120° C. (0.02 mmHg) to yield 2.2 g.of yellow oil (32% yield) indentified as 2'-methoxy,6'-methyl-N-[(2-methylbutoxy)methyl]-2-chloroacetanilide.

Anal. Calc'd. for C₁₆ H₂₄ ClNO₃ : C, 61.24; H, 7.71; Cl, 11.30; Found:C, 61.29; H, 7.76; Cl, 11.35.

In similar fashion the process described above was used to prepare thecompounds identified in Table 1 below; said process maybe schematicallyillustrated as: ##STR17##

In the examples shown in Table I below, X₁ is equal to chloro and n isequal to zero.

                                      TABLE 1                                     __________________________________________________________________________    Exam-                                                                         ple                                                                           Num-                           mp   b.p.  %   Empirical                                                                             Analysis                ber R           R.sub.2  R.sub.3                                                                             °C.                                                                         °C.                                                                          Yield                                                                             Formula Calc'd.                                                                            Found              __________________________________________________________________________    2   CH.sub.2 CCH                                                                              OCH.sub.3                                                                              CH.sub.3                                                                            75-76                                                                              --    54  C.sub.14 H.sub.16 ClNO.sub.3                                                  5       C                                                                                  59.58                                                                    H                                                                                  5.76                                                                     Cl                                                                                 12.53              3   CH.sub.2 CH.sub.2 (CH.sub.2).sub. 3 CH.sub.3                                               ##STR18##                                                                             CH.sub.3                                                                            --   120° @ 0.08mmHg                                                              94  C.sub.18 H.sub.28 ClNO.sub.3                                                  2                                    ##STR19##  OCH.sub.3                                                                              CH.sub.3                                                                            --   130° @ 0.04mmHg                                                              78  C.sub.18 H.sub.                                                               28 ClNO.sub.3                                                                         C 63.24 H 8.26 Cl                                                             10.37                                                                              63.55 7.80                                                                    10.50              5   CH.sub.2CHCHCl                                                                            OCH.sub.3                                                                              CH.sub.3                                                                            --   123° @                                                                        89%                                                                              C.sub.14 H.sub.17 Cl.sub.2                                                    NO.sub.3                                                                              C                                                                                  52.79                                                  0.03mmHg          H                                                                                  5.44                                                                     Cl                                                                                 21.79              6   CH.sub.2 CH.sub.2 OCH.sub.3                                                               OC.sub.2 H.sub.5                                                                        ##STR20##                                                                          --   130° @ 0.04mmHg                                                              88  C.sub.17 H.sub.26 ClNO.sub.4                                                  .       C 59.38 H 7.62 Cl                                                             10.31                                                                              59.38 7.62                                                                    10.32              7   CH.sub.2 CHCH.sub.2                                                                       O(CH.sub.2).sub.5 CH.sub.3                                                             CH.sub.3                                                                            --   133° @                                                                       69  C.sub.19 H.sub.28 ClNO.sub.3                                                          C                                                                                  64.55                                                  0.03mmHg          H                                                                                  8.02                                                                     Cl                                                                                 10.07              8                                                                                  ##STR21##  OCH.sub. 3                                                                             CH.sub.3                                                                            --   105° @ 0.03mmHg                                                              97  C.sub.16 H.sub.24 ClNO.sub.2                                                          C 61.24 H 7.71 Cl                                                             11.30                                                                              61.04 7.63                                                                    11.35              9   CH.sub.2 CH.sub.2 Cl                                                                      OCH.sub.3                                                                              CH.sub.3                                                                            --   129° @                                                                       98  C.sub.13 H.sub.17 Cl.sub.2                                                    NO.sub.3                                                                              C -- --                                                     0.05mmHg          H -- --                                                                       Cl                                                                                 --                 10                                                                                 ##STR22##                                                                                 ##STR23##                                                                             H     --   --    --  C.sub.17 H.sub.26 ClNO.sub.3                                                          C 62.28 H 7.99 Cl                                                             10.87                                                                              62.41 8.04                                                                    10.70              11                                                                                 ##STR24##  OCH.sub.3                                                                              CH.sub.3                                                                            --   200° @ 0.4mmHg                                                               --  C.sub.17 H.sub.24 ClNO.sub.4                                                          C 59.73 H 7.08 Cl                                                             10.37                                                                              59.64 7.10                                                                    10.37              12                                                                                 ##STR25##  OCH.sub.3                                                                              CH.sub.3                                                                            --   130° C. @ 0.02mmHg                                                           100 C.sub.16 H.sub.22 ClNO.sub.3                                                          C 61.63 H 7.11 Cl                                                             11.37                                                                              61.55 7.11                                                                    11.27              13                                                                                 ##STR26##  OCH.sub.3                                                                              CH.sub.3                                                                            --   --    --  C.sub.17 H.sub.26 ClNO.sub.3                                                          C -- H -- Cl                                                                       -- -- --           14  (CH.sub.2).sub.2 CH.sub.3                                                                 NO.sub.2 NO.sub.2                                                                            --   --    93  C.sub.12 H.sub.14 ClN.sub.3                                                   O.sub.6 C                                                                                  43.41                                                                    H                                                                                  5.29                                                                     N                                                                                  12.20              15  C.sub.2 H.sub.5                                                                           NO.sub.2 CH.sub.3                                                                            96-98                                                                              --    --  C.sub.12 H.sub.15 ClN.sub.2                                                   O.sub.4 C                                                                                  50.27                                                                    H                                                                                  5.27                                                                     N                                                                                  9.75               16  C.sub.2 H.sub.5                                                                           NO.sub.2 H     63-65                                                                              --    48  C.sub.11 H.sub.13 ClN.sub.2                                                   O.sub.4 C                                                                                  48.51                                                                    H                                                                                  4.82                                                                     N                                                                                  10.25              17                                                                                 ##STR27##  NO.sub.2 H     --   --    66  C.sub.13 H.sub.17 ClN.sub.2                                                   O.sub.4 C 51.92 H 5.70 N                                                              9.31 50.62 5.83                                                                    9.21               18  CH.sub.3    NO.sub.2 NO.sub.2                                                                            105.5-108                                                                          --    80  C.sub.10 C.sub.10 ClN.sub.2                                                   O.sub.6 C                                                                                  39.42                                                                    H                                                                                  3.22                                                                     N                                                                                  14.22              __________________________________________________________________________

Example 19 illustrates the use of HCl as the acid halide.

EXAMPLE 19 Preparation of2'-Methoxy-6'-Methyl-N-(Isorpropoxy)methyl-2-chloroacetanilide

2.8 g. of isopropanol and 1.5 g. of paraformaldehyde were added to 100ml. of methylene chloride and the mixture treated with gaseous HCl atroom temperature. To this mixture was added 5.0 g. of2'-methoxy-6'-methyl-2-chloroacetanilide and 2.0 g. of phase transfercatalyst at 25° C. Thereafter, 25 ml. of 50% NaOH was added in oneportion and the temperature of the reaction mixture rose to 37° C. Themixture was cooled to 26° C. and stirred for 40 minutes, whereupon GLCshowed the reaction complete. 100 ml. of cold H₂ O was added tofacilitate separation and the organic layer was washed once with H₂ O,dried over MgSO₄, evaporated and Kugelrohr distilled, b.p. 180° C. (0.05mmHg) to yield an oil identified as2'-methoxy,6'-methyl-N-(isopropoxy)methyl-2-chloroacetanilide.

Anal. Calc'd. for C₁₃ H₁₈ ClNO₃ : C, 57.46; H, 6.68; Cl, 5.51; Found: C,57.32; H, 6.72; Cl, 5.13.

Example 20 and the examples shown in Table II below, illustrate thepreparation of 2-haloacetanilide compounds wherein R₁ is C₁₋₅ alkoxy(C₁₋₅) alkoxy or C₁₋₅ alkoxy (C₁₋₅) alkoxy (C₁₋₅) alkoxy.

EXAMPLE 20 Preparation of2'-[(2-Ethoxy)ethoxy]-6'-Isopropyl-N-(Ethoxy)methyl-2-chloroacetanilide

A mixture containing ethyl alcohol (5.75 g; 0.125 mole) andparaformaldehyde (1.86 g; 0.062 mole) in 100 ml. of methylene chloridewas cooled to 5° C. To the cooled mixture was added acetyl bromide (7.56g; 0.062 mole) and the resulting mixture was stirred for 45 minutes. Tothe resulting mixture was added a mixture containing2-[(2-ethoxy)ethoxy]-6'-isopropyl-2-chloroacetanilide (4.5 g; 0.015mole), 1.5 g. of benzyltriethylammonium bromide (phase transfercatalyst) in 75 ml. of methylene chloride. While maintaining thetemperature of the reaction mixture at 15° C., 45 ml. of a 50% solutionof sodium hydroxide was added to the reaction mixture and the resultingsolution was stirred for 2 hours. To the resulting mixture was added 100ml. of cold water. The layers were separated and the organic layer waswashed with water, dried over magnesium sulfate and concentrated invacuo to yield a crude product. The crude product was distilled at 128°C. (0.03 mmHg) to yield2'-[(2-ethoxy)ethoxy]-6'-isopropyl-N-(ethoxy)methyl-2-chloroacetanilide(4.4 g; 80% yield) as a yellow liquid; b.p., 128° C. @ 0.03 mmHg.

Anal. Calc'd. for C₁₈ H₃₁ ClNO₄ : C, 60.41; H, 7.89; Cl, 9.91; Found: C,60.36; H, 7.91; Cl, 9.92.

In a similar fashion other compounds were prepared. The data for saidcompounds is summarized in Table II below.

                                      TABLE II                                    __________________________________________________________________________     ##STR28##                                                                    __________________________________________________________________________    Example                                    b.p.  Analysis                     Number                                                                             R.sub.2           R.sub.3                                                                              R        X.sub.1                                                                           (C.°)                                                                        Element                                                                            Calc'd                                                                             Found              __________________________________________________________________________    21   O(CH.sub.2).sub.2OCH.sub.3                                                                      CH(CH.sub.3).sub.2                                                                   CH.sub.2 CH.sub.2 CH.sub.3                                                             Br  125° C.                                                                      C    60.41                                                                              60.39                                                         0.03 mmHg                                                                           H    7.89 7.90                                                                Cl   9.91 9.94               22   O(CH.sub.2).sub.2OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                    CH.sub.2 CH.sub.3                                                                      Br  125° C.                                                                      C    58.27                                                                              58.30                                                         0.03 mmHg                                                                           H    7.33 7.39                                                                Cl   10.75                                                                              10.76              23   O(CH.sub.2).sub.2OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                    CH(CH.sub.3).sub.2                                                                     Br  127° C.                                                                      C    59.38                                                                              59.39                                                         0.04 mmHg                                                                           H    7.62 7.63                                                                Cl   10.31                                                                              10.29              24   O(CH.sub.2).sub.2OCH.sub.3                                                                      CH.sub.2 CH.sub.3                                                                    CH.sub.2 CH.sub.2 CH.sub.3                                                             Br  125° C.                                                                      C    59.38                                                                              59.40                                                         0.03 mmHg                                                                           H    7.62 7.63                                                                Cl   10.31                                                                              10.30              25   O(CH.sub.2).sub.2OCH.sub.2 CH.sub.3                                                             H      CH.sub.2 CH.sub.2 CH.sub.3                                                             Cl  124° C.                                                                      C    58.27                                                                              58.31                                                         0.03 mmHg                                                                           H    7.33 7.36                                                                Cl   10.75                                                                              10.70              26   O(CH.sub.2).sub.2OCH.sub.2 CH.sub.3                                                             H      CH.sub.2 CH(CH.sub.3).sub.2                                                            Cl  131° C. @                                                                    C    59.38                                                                              59.32                                                         0.02 mmHg                                                                           H    7.62 7.60                                                                Cl   10.31                                                                              10.32              27   O(CH.sub.2).sub.2OCH.sub.2 CH(CH.sub.3).sub.2                                                   CH.sub.3                                                                             CH.sub.2 CH.sub.3                                                                      Cl  126° C.                                                                      C    60.41                                                                              60.31                                                         0.03 mmHg                                                                           H    7.89 7.89                                                                Cl   9.91 9.89               28   O(CH.sub.2).sub.2OCH.sub.2 CH(CH.sub.3).sub.2                                                   CH.sub.3                                                                             CH.sub.2 CH.sub.2 Cl.sub.3                                                             Cl  162° C.                                                                      C    55.11                                                                              55.02                                                         0.03 mmHg                                                                           H    6.94 6.97                                                                Cl   18.07                                                                              18.01              29   O(CH.sub.2).sub.2OCH.sub.2 CH(CH.sub.3).sub.2                                                   CH.sub.3                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                             Cl  143° C.                                                                      C    61.36                                                                              61.47                                                         0.03 mmHg                                                                           H    8.13 8.15                                                                Cl   9.53 9.51               30   OCH.sub.2O(CH.sub.2).sub.2OCH.sub.3                                                             H      CH.sub.2 CH.sub.3                                                                      Cl  145°  C.                                                                     C    54.30                                                                              54.31                                                         0.06 mmHg                                                                           H    6.68 6.67                                                                Cl   10.69                                                                              10.63              31   OCH.sub.2O(CH.sub.2).sub.2OCH.sub.3                                                             H      CH.sub.3 Cl  140° C.                                                                      C    52.92                                                                              52.90                                                         0.07 mmHg                                                                           H    6.34 6.34                                                                Cl   11.16                                                                              11.15              __________________________________________________________________________    Example                                    b.p.  Analysis                     Number                                                                             R.sub.2           R.sub.3                                                                              R'       X'  (C.°)                                                                        Element                                                                            Calc'd                                                                             Found              __________________________________________________________________________    32   O(CH.sub.2).sub.2O(CH.sub.2).sub.2OCH.sub.3                                                     CH.sub.3                                                                             CH.sub.2 CH.sub.3                                                                      Cl  160° C.                                                                      C    56.71                                                                              56.81                                                         0.08 mmHg                                                                           H    7.28 7.32                                                                Cl   9.85 9.88               33   O(CH.sub.2).sub.2OCH.sub.2 CH.sub.3                                                             CH(CH.sub.3).sub.2                                                                   CH(CH.sub.3).sub.2                                                                     Cl  125° C.                                                                      C    61.36                                                                              61.28                                                         0.05 mmHg                                                                           H    8.13 8.17                                                                Cl   9.53 9.52               __________________________________________________________________________

What is claimed is:
 1. A process for preparing haloalkyl ethers havingthe formula ##STR29## where R₁ is alkyl containing 1 to 4 carbon atoms;X is chloro, bromo or iodo; R is alkyl containing 1 to 10 carbon atoms,alkenyl containing 3 to 10 carbon atoms, cycloalkyl containing 3 to 10carbon atoms, alkynyl containing 3 to 10 carbon atoms, (C₁₋₅) alkoxy(C₂₋₅) alkyl, mono-halo (C₂₋₅) alkyl, mono-halo (C₃₋₅) alkenyl or##STR30## y is the integer 2, 3, or 4, with the proviso that when R isalkenyl or alkynyl the carbon atom attached to the oxygen may not sharea double or triple bond with an adjacent carbon atom;which comprisesreacting an alcohol of the formula

    ROH                                                        (II)

(where R is as defined in Formula I); with an aldehyde of formula##STR31## (where R₁ is as defined in Formula I); in the presence of asolvent and in the presence of a halide liberating ion compound of theformula ##STR32## where X is as defined in Formula I and where R₅ isC₁₋₅ alkyl, phenyl or benzyl; the temperature of said reaction beingfrom about -20° C. to 100° C.
 2. A process according to claim 1 whereinsaid halide liberating ion compound is ##STR33##
 3. A process accordingto claim 2 wherein said halide liberating ion compound is ##STR34##
 4. Aprocess according to claim 1 wherein said solvent is methylene chloride.5. A process according to claim 1 wherein R is alkyl containing 1 to 10carbon atoms.
 6. A process according to claim 1 wherein R is alkylcontaining 3 to 10 carbon atoms.
 7. A process according to claim 1wherein R is alkenyl containing 3 to 10 carbon atoms, cycloalkylcontaining 3 to 10 carbon atoms, alkynyl containing 3 to 10 carbonatoms, (C₁₋₅) alkoxy (C₂₋₅) alkyl, mono-halo (C₂₋₅) alkyl, mono-halo(C₃₋₅) alkenyl or ##STR35## y is the integer 2, 3, or
 4. 8. A processaccording to claim 1 wherein the temperature of said reaction is fromabout 5° C. to about room temperature.
 9. A process according to claim 1wherein the temperature of the reaction is from about 10° to about 50°C.